Process for the dyeing of polyethylene glycol terephthalate-type polyester fibers



United States Patent ()fi ice 3,377,129 PRQCESS FOR THE DYEING FPOLYETHYLENE GLYCUL TEREPHTHALATE-TYPE POLYESTER FlBERS Hans E.Wegmiiller and Werner Bossard, Riehen, Switzerland, assignors to .l'. R.Geigy A.G., Basel, Switzerland No Drawing. Original application Aug. 17,1964, Ser. No. 390,232, now Patent No. 3,341,512, dated Sept. 12, 1967.Divided and this application Jan. 12, 1967, Ser No. 623,785 Claimspriority, application Switzerland, Sept. 9, 1963, 11,094/63 5 Claims.(Cl. 8-41) ABSTRACT OF THE DISCLOSURE Polyethylene glycolterephthalate-type fibers and materials made therefrom are excellentlydyed with a new group of dyestuffs which correspond to the formula Y1 3oo-N\ o o- NOz wherein X is lower alkoxy or phenoxy, Y is H, loweralkyl, lower alkoxy, Cl, Br or N0 and R is lower alkyl or loweralkoxyalkyl.

The present application is a division of copending application, Ser. No.390,232, filed August 17, 1964.

This invention relates to the dyeing of polyethylene glycolterephthalate type fibers with new, difiicultly watersoluble dyestuffssuitable for the dyeing of such fibers and of textile materials madetherefrom, as well as to the aforesaid fibers and textile materialswhich have been dyed with the aid of these dyestuffs.

Dyeing as used in this specification and in the appended claims alsocomprises pad-dyeing and printing.

In the dyeing of polyethylene glycol terephthalate ty pe textilepolyester fibers and fabrics made therefrom, it has been a specialproblem that dyeings with disperse dyes which are fast to light andsublimation, and at the same time satisfactorily reserve cellulose andnatural polyamide fibers, especially cotton or wool, are difiicult toobtain, because those dyestuffs which promise to fulfill the aboverequirements, often do not draw sufiiciently on the aforesaidterephthalate type fibers, and/or lack depth of color; on the otherhand, dyestuffs which draw satisfactorily on the last-mentioned fibersoften lack some or all of the first-mentioned properties.

It is also known that non-sulfonated disperse dyes of thebenzene-azo-barbituric acid series, especially when substituted at thebenzene nucleus, e.g. by alkoxy or aryloxy radicals, and dyestuffs ofthe benzene-azothiobar-bituric acid series, especially those which aresubstituted at the benzene nucleus by a nitro group, are valuable dyesfor hydrolyzed and also for unhydrolyzed cellulose acetate, cellulosepropionate and others, as well as for mixed organic acid esters ofcellulose.

Generally, the disperse dyes falling under the second of the aboveseries, cannot be used for the dyeing of polyethylene glycolterephthalate fibers because they do not withstand the conditions ofdyeing of the latter fibers, especially in the so-called hightemperature dyeing process 3,377,129 Patented Apr. 9, 1968 whichrequires dyeing at temperatures above C. under excess pressure, while onthe other hand the known disperse dyes of the first-menti0nedbenzene-azo-bar-bituric acid series generally lack drawing power and/ordepth of color in dyeings 0n polyethylene glycol terephthalate fibers tosuch an extent that they are not commercially useful for dyeing thesefibers.

Polyethylene glycol terephthalate type polyester fibers as used in thisspecification and the appended claims, comprise such well knownterephthalate and iso-phthalate fibers as Terylene, Kodel, Vycron andthe like.

The term lower as used in this specification and in the appended claimsin connection with alkyl or alkoxy means that these radicals have from 1to 4 carbon atoms.

Other specific problems are created in the well-known high-temperaturedyeing of polyethylene glycol terephthalate type fibers, namely, above100 C. under pressures above atmospheric, especially when the use ofswelling agents is to be dispensed with. Under these high temperatureconditions many otherwise satisfactory disperse dyes fail to showsatisfactory drawing power on the aforesaid fibers. In these cases,there is danger that the dyestuff particles in aqueous dispersions ofsuch disperse dyes will agglomerate and excess of dyestutf which has notproperly drawn on the fibers, will be deposited thereon and will thusdetrimentally influence the fastness properties of the resulting dyeingson polyethylene glycol terephthalate fiber materials, especiallyfastness to crocking and to organic solvents.

We have now found that dyes of the formula wherein R represents loweralkyl or lower alkoxy-lower alkyl, X represents lower alkoxy, especiallymethoxy or ethoxy, or phenoxy, and Y represents hydrogen, lower alkyl,especially methyl or ethyl, lower alkoxy, especially methoxy or ethoxy,chlorine, bromine or nitlo, are distinguished as polyterephthalate fiberdyes because they possess excellent drawing power on these fibersequally in the carrier dyeing process, below 100 C. with the use ofswelling agents as well as under the conditions of the high temperatureprocessoutlined above. The dyeings obtained therewith possess very goodfastness to light and to sublimation, to crocking and to organicsolvents; they reserve cotton and Wool well; moreover in mixture withblue dyestuffs they yield dyeings of level green shades, an advantagewhich is lacking in many of the known disperse polyterephthalate fiberdyes.

These good dyeing properties of the dyestuffs of Formula IE onpolyethylene glycol terephthalate type fibers are particularlyunexpected, since the aforesaid dyestuffs are of no practical value ascellulose ester dyes, for they do not possess any practically usefuldrawing power on such fibers.

The compounds of Formula IB are produced by coupling the diazonium saltof an amine of the formula wherein X is as precedingly defined, with acoupling component of the formula (III) wherein Y and R are asprecedingly defined, with malonic acid, advantageously in an inertorganic solvent such as chloroform, in the presence of an agent whichsplits off water, e.g. in the presence of phosphorus oxychloride, or byreactionof the above N,N-disubstituted urea with cyanoacetic acid toform the corresponding cyanoacetyl urea, conversion of this in analkaline medium to form the 4-aminouracil and saponification of theimino group to the x0 group, e.g. with boiling diluted hydrochloricacid.

The diazonium salt of an amine of Formula II is coupled with thecoupling component of Formula III by the usual methods, preferably in amineral acid to weakly acid aqueous medium, in particular at a pH of 4to 4.5. If the coupling is made in a :mineral acid medium, the acid isadvantageously buffered, e.g. with alkali metal salts of low fattyacids.

The dyestuffs according to the invention are brought into afinelydispersed form by millingwith dispersing agents. Suitable dispersingagents are, e.g. anionic dispersing agents such as alkylaryl sulfonates,condensation products of formaldehyde and naphthalene sulfonic acids,lignin sulfonates, or non-ionogenic dispersing agents .such as fattyalcohol polyglycol ethers. Advantageously mixtures of the anionic andnon-ionogenic dispersing agents mentioned are used.

When so prepared, the dyestuffs according to the invention are suitablefor the dyeing of polyethylene glycol terephthalate type fibers from anaqueous dispersion.

Polyglycol terephthalate fibers are dyed with aqueous dispersions of thedyestuffs according to the invention preferably at temperatures of over100" C. under pressure above atmospheric,.preferably at 0.5 to 4atmospheres excess pressure. Dyeing can also be performed, however,under ambient pressure at the boiling point of the dyebath in thepresence of carriersv such as phenylphenol, polychlorobenzene compoundsor similar auxiliaries, or pad dyeing can be performed on the foulardfollowed by thermo-fixing at 180-210 C.

On the fibers mentioned, the dyestuffs according to the inventionproduce greenish yellow, yellow and orange dyeings which have excellentfastness to washing, milling, sublimation, light, rubbing, perspiration,solvents, crossdyeing, decatizing, gas fading and industrial fumes. Inaddition, vegetable and animal fibers, particularly cotton or wool, arevery well reserved by the dyestuffs according to the invention. Also,they can be evenly dyed with the usual commercial carriers. Good andevenly penetrated dyeings are obtained with these dyestuffs even onclosely woven fabric or tightly twisted yarns.

The following non-limitative examples illustrate the invention. Wherenot expressly otherwise stated, parts and percentages are given byweight. The temperatures are in degrees centigrade. The relationship ofparts by weight to parts by volume is that of grams (g.) to milliliters(ml.).

Example 1 A fine suspension of 16.8 parts of1-amino-2-nitromethoxybenzene in 500 parts of water, 60 parts of 36%hydrochloric acid and 5 parts of cetyl polyglycol ether is diazotised inthe usual way at 05- by the addition of 6.9 parts of sodium nitrite. Thediazonium salt solution is clarified and, at 0-5", is added to asolution of 21.8 parts of 1-phenyl-3-methyl.barbituric acid in 800 partsof water and 200 parts of acetic acid. The pH of the coupling bath isthen raised to 4-4.5 by the addition of sodium acetate. On completion ofthe coupling, the yellow precipitate formed, the composition of whichcorresponds to the formula is filtered off, washed with a lot of waterand dried in vacuo at 6070. After milling with the sodium salt of acondensation product of naphthalene-Z-sulfonic acid and formaldehyde,the dyestuff so obtained dyes polyglycol terephthalate fibers from anaqueous dispersion, optionally in the presence of a carrier such as thesodium salt of o-phenylphenol, in pure yellow shades. The dyeings havevery good fastness to washing, rubbing, light and sublimation.

Dyestuffs which have similar properties are obtained if the diazocomponents given in Column 2 of the following Table I are coupled underthe conditions described in the above example with the equimolecularamount of one of the coupling components given in Column 3.

barbituric aeid.

Example 8 2 parts of'the dyestuff prepared according to Example 1 aredispersed in 4000 parts of water. 20 parts of the sodium salt ofo-phenylphenol as swelling agent as well as 20 parts of diammoniumsulfate are added to this dispersion which is then used to dye 100 partsof polyethylene glycol terephthalate yarn for minutes at to 98. The dyeliquor is almost completely exhausted. The dyeing is rinsed with waterand then after-treated for 15 minutes at 80 with 12 parts of 30%-sodiumhydroxide solution and 4 parts of octylphenyl polyglycol ether in 4000parts of water. Finally the dyed material'is again thoroughly rinsedwith water and dried.

In this manner, a yellow dyeing is obtained which is fast to washing,light and sublimation.

When, in the above example, the 20 parts of the sodium salt ofo-phenylphenol are replaced by 20 parts of one of the followingcommercially available swelling agents, namely 20 parts of-o-phenylphenol emulsion, or

20 parts of p-chlorophenoxyethanol emulsion, or

20 parts of dichlorobenzene emulsion, or

20 parts of cresotic acid methyl ester emulsion, or by 20 parts of a 1:1emulsion of terephthalic acid dimethyl ester and benzanilide,

while all other conditions are the same as in the above example, yellowdyeings of equal quality are obtained.

When, in the above example, the 100 parts of polyethylene glycolterephthalate yarn are replaced by 100 parts of polyethylene glycolisophthalate yarn or ,100 parts of polycyclohexanediol terephthalatefibers and dyeing is performed under the same conditions as before,yellow dyeings of equal quality are obtained.

Dyeings of similarly good quality are obtained when, in the aboveexample, the 2 parts of the dyestufi" prepared according to Example 1are replaced by 2 parts of the dyestuff prepared as described inExamples 2 to 7.

Example 9 A fine suspension of 16.8 parts of 1-amino-2-nitro-4-methoxy-benzene in 500 parts of water, 60 parts of 36%- hydrochloricacid and 5 parts of cetyl polyglycol ether is. diazotized in the usualWay at to by the addition of 6.9 parts of sodium nitrite. 1

Separately 25.3 parts of 1-(3-ch1orophenyl)-3-methylbarbit-uric acid aredissolved in 300 parts of water by the addition of 8 parts of sodiumhydroxide. The alkaline 1-(3'-chlorophenyl)-3-methyl-barbituric acidsolution is added dropwise at 0 to 5 to the prepared diazonium saltsolution. Then the pH-value of the coupling bath is adjusted to 4 to 4.5by the addition of sodium acetate. On completion of the couplingreaction, the yellow precipitate corresponding to the formula CO-N N02CH3 is separated by filtration, washed with water and dried in vacuo at70 to 80. 10 parts of the coupling product thus obtained are broughtinto fine water-dispersible form by milling them together with thesodium salt of a condensation product of naphthalene-Z-sulfonic acidformaldehyde and 10 parts of a lignin sulfonate. The aqueous dispersionof the dyestutf worked up in this manner is very stable and when used inparticular for dyeing polyethylene glycol terephthalate slubbings, yarnand fabrics at 125 to 130 under pressure, it has no tendency toprecipitate.

The 1-(3-chlorophenyl)-3-methylbarbituric acid used as couplingcomponent in this example is prepared, for instance, by reactingN-(35-chlorophenyl)-N'-methyl-urea with cyanoacetic acid to form thecorresponding cyanoacetyl urea, converting the cyano-acetyl urea withsodium hydroxide to form l-(3-chl0rophenyl)-3-methyl-4-aminouracil andthen splitting oif the amino group in diluted boiling hydrochloric acid.Pure 1-(3'-chlorophenyl)-3- methyl-barbituric acid having a meltingpoint of 162 to 163 is obtained from the crude product bycrystallization from ethanol.

Dyestuffs of similar properties are obtained when the diazo componentslisted in Column 2 of the following Table II are reacted under theconditions described above with one of the coupling components mentionedin Col-- umn 3 and when the resulting coupling products are broughtunder the above-described conditions into fine water-dispersible form.

TABLE II Shade on poly- Ex. Dlazo component Coupling componentethylene-glycol N o. tereph th alatc fibers 10. 1 amin0-2-nitro-41-(2-1nethylphenyl)- Yellow.

methoxybenzene. SqniethyI-baIbituric 8C1 11 do 1-(3,4-dichlor0phenyl)-Do.

3-rnethyl-barbituric acid. 12 do 1-(4-brom0phenyl)-3- Do.

methoxypropyl-barbituric acid. 13 lo 1-(4-chl0ropheny1)-3- D0.

ethyl-barbituric acid. 14.- -do 1(3-rnethylpheny1)-3- D0.

n-propyl-barbituric acid. 15. e l-amin02-nitro-4- 1-(3-n1ethylphenyl)-3- Do.

ethoxy-beuzene. mettihyl-barbituric acl 16 .do 1-(3-nitrophenyl)-3- Do.

methyl-barbituric acid. 17 do 1-(2-methyl5-chloro- Do.

phenyD-dmethylbarbiturio acid. 18 do 1(2,4-din1ethyl- Do.

phenyD-tl-Inethylbarbituric acid. 19. 1. do 1-(2 methoxyphenyl)-3- Do.

methyl-barbituric acid. 20. 1-an1in0-2-nitro-4- 1-(z-n1ethylphenyl)-3-Do.

phenoxy-benzene. meghyl-barbituric aci 21 do 1(3-chlorophenyl)-3- Do.

methyl-barbituric acid.

Example 22 3 parts of the dyestuif prepared according to Example 20 aredispersed in 4000 parts of water. 2 0 parts of the sodium salt ofo-phenylphenol as swelling agent as well as 20 parts of diammoniumsulfate are added to the dispersion which is then used to dye for 90minutes at 95 to 98, 100 parts of polyethylene glycol terephthalateyarn. The dyeing is rinsed and then aftertreated for 15 minutes at with12 parts of 30%-sodium hydroxide solution and 4 parts of octyl phenylpolyglycol ether in 4000 parts of water. Subsequently, the dyed yarn isagain thoroughly rinsed with water and dried. In this manner, a pureyellow dyeing is obtained which has a very good fastness to light When,in the above example, the 100 parts of polyethylene glycol terephthalateyarn are replaced by 200 parts of a blended fabric consisting of cottonand polyethylene glycol terephthalate (ratio 1:1), while the otherconditions are maintained, the polyethylene glycol terephthalate threadsare dyed in the same pure yellow as above while the cotton threads arevery well reserved.

The dyestuffs descn'bed in the other examples have similar goodqualities in reserving cotton when used to dye a blendedcotton/polyethylene glycol terephthalate fabric.

' Example 23 3' parts of the dyestuif prepared according to Example 10are dispersed in 4000 parts of water. 20 parts of the sodium salt ofo-phenylphenol as swelling agent as well as 20 parts of diammoniumphosphate are added to this dispersion which is then used to dye forminutes at to 9'8. 200 parts of a blended fabric consisting of 55% ofwool and 45% of polyethylene glycol terephthalate. The dyeing is rinsedwith Water and then aftertreated for 15 minutes at 60 with 4 parts ofoctylphenyl polyglycol ether in 4000 parts of water. Then the dyedfabric is again thoroughly rinsed with water and dried. Under theseconditions, the polyethylene glycol terephthalate fibers of the blendedfabric are dyed in a pure yellow shade 'while the woollen portion iswell reserved.

The dyestuifs described in the other examples have similar goodproperties in reserving the woollen part when used for the dyeing ofblended wool/polyethylene glycol terephthalate fabrics.

7 Example 24 0.5 part of the dyestulf obtained according to Example 9are dispersed in 1000 parts of water in a pressure dyeing apparatus. 0.3part of oleic acid N-methyltauride, 0.5 part of the sodium salt of acondensation product of naphthalene-Z-sulfonic acid and formaldehyde, 2parts of diammonium sulfate as well as 0.1 part of 85%-formic acid areadded to this dispersion.

parts of densely wound polyethylene glycol terephthalate yarn areintroduced at 50, the closed bath is heated within minutes to 125 to 130and is maintained at this temperature for another 45 minutes while thegoods are being dyed under pressure. The dyebath is well exhausted. Thedyeing is rinsed with water, soaped and dried. A yellow dyeing isobtained which has good fastness to washing, rubbing, perspiration,light, sublimation and solvents, and which is free from any visibledyestuif residue.

Similar good results are obtained when, in the above example, the 0.5part of the dystuff prepared according to Example 9 is replaced by 0.5part of the dyestuffs prepared according to the Examples 10 to 21 anddyeing is performed under the conditions described above on polyethyleneglycol terephthalate, polycyclohexane diolterephthalate or polyethyleneglycol isophthalate slubbings, yarn or fabric.

Example 25 Polyethylene glycol terephthalate fabric is printed on aprinting machine at 25 with a liquor of the following composition:

parts of the dyestuff prepared according to Example 14 finely dispersedin 300 parts of water 40 parts of urea 400 parts of crystal gumthickener and 200 parts of a 10% aqueous p-phenylphenol emulsion Theprinted fabric is steamed for minutes at and then soaped, rinsed wthwater and dried.

A yellow colored printing is obtained good fastness to washing,rubbing,light and sublimation.

A printing of similar good quality is obtained-when in the above examplethe 200 parts of 10% p-phenylphenol emulsion are replaced by 200 partsof water and. the.

Example 26 Polyethylene glycol terephthalate fabric is impregnated on afoulard at 40 with a bath of the following, composition:

20 parts of the dyestulf prepared according to 19, finely dispersed in-Example 7.5 parts of sodium alginate 20 parts of triethanolamine 20parts of octylphenyl polyglycol ether and 900 parts of water.

The fabric is squeezed to about 100% moisture content, dried at 100 andthen fixed for 30 seconds with air at a temperature of 210. Thedyedgoodsare then rinsed with water, soaped and dried. Undertheseconditions, a

which has very.

yellow dyeing is obtained which is fast to washing, rubhing, light, andsublimination.

We claim:

1. A process for the dyeing of polyethylene glycol terephthalate-typepolyester fibers, comprising dyeing the aforesaid fibers with an aqueousdispersion of a dyestuff of the formula wherein X is lower alkoxy orphenoxy, Y is H, lower alkyl, lower alkoxy, Cl, Br or. N0 and R is loweralkyl or lower alkoxyalkyl.

2. A process according to claim 1, wherein the dyestuff is the dyestuffof the formula 3. A process according to claim 1, wherein the dyestuffis the dyestuff of the formula I CO- N02 4. A process according-to claim1, wherein the dyestuff is thedyestuff of the formula CON I a 5. Aprocess according to claim 1, wherein the dyestulf is the dyestuff ofthe formula NORMAN G. TORCHIN, Primary Examiner. T, J. HERBERT, JR.,Assistant Examiner.

